Mono- and disazo dyestuffs containing a diazine or triazine group



U.S. ,Cl. 260-154 United States Patent ABSTRACT. OF THE DISCLOSURE Azo dyestuffs of the formula:

- I IIIHR Y -OH The present application is concerned with valuable new azo dyestuffs of the formula Q awn,

in which Y stands for a sulphonic acid group or an optionally substituted sulphonamide group, X is a hydrogen atom or a sulphonic acid group, R- represents a in which R, has the same meaning as above, with 1 mol of a coupling component of the formula NHR Y -on X (111) in which R, X and Y have the meaning already given, or by coupling the tetrazo compound of a diamine of the formula in which R has the same meaning as above, with 2 mol of a coupling component of the Formula III. The coupling is carried out in an acid, preferably aqueous hydrogen atom or an, optionally,substituteds alkyl radical, W

R stands for the radical of a diazo or tetrazo component containing a sulphone group and/or a sulphonic acid group, and n is the number 1 or 2.

A particularly valuable group of dyestuffs within the range of the Formula I corresponds to the formula wherein R' is the radical of sulphone groupand/or sulphonic acid group-containing diazo component of the benzene or naphthalene series, and n has the same meaning as above.

The new dyestuffs are obtained by combining the diazo compound of an amine of the formula medium and takes place in the peri-position to the hydroxyl group or in the oc-POSllllOIl, adjacent to the NHR group, of the naphthalene component (III).

The procedure can also be carried out by using, instead of the diazo compound of an amine of the formula R -NH the diazo compound of an amine of the formula R -NH in which R means an aromatic radical which contains a sulphone and/or a sulphonic acid group and which can be converted into the radical R by reactions customary in azo chemistry, such as reduction, hydrolysis, acylation and/ or condensation, and then converting the radical R into the radical R after coupling.

The dyestuffs (II), preferred within the range of the dyestuffs of the Formula I, can be obtained in an analogous manner by coupling the diazo compounds of the above-mentioned amines with 2-amino-8-hydroxy-naphthalene-S-sulphonic acid.

Coupling components of the Formula III which contain only one sulphonic acid group are described, for example, in British patent specification No. 5148 (1894); (cf. N. Donaldson The Chemistry and Technology of Naphthalene Compounds, p. 323). The 2-amino-8-hydroxynaphthalene-5,7-disulphonic acid can be obtained by sulphonating the 5- or 7-mono-sulphonic acid.

Diazo components R -NH suitable for the production of monoazo dyestuffs, in which in Formula I n stands for the number 1, are, for example, 4-amino-4'- acylaminodiphenyl 3-sulphonic acids (acyl being e.g. vacetyl, propionyl, fumaroyl, benzoyl, mor .p-ehlorobenzoyl, m-' or p-toluyl, mor pnitrobenzoyl, m-trifluoromethylbenzoyl, terephthaloyl, isophthaloyl, benzenes'ul-phonyl or a benzenesulphonyl'radical substituted -in thebenzene nucleus), asymmetrical ureas, such as N-phenyl-N,4-( 4-aminodiphenyl 3 sulphonic acid)- urea, which may be substituted in the phenyl nucleus for example by chlorine in the por m-position, aminophenyl ureas of the formula in which T means hydrogen or substituents, such as e.g.

chlorine.

Amino compounds of the formula 3 4 nicotinoyl radical, the 2,3 dichloro quinoxalinoyl-(6)- characterised by good fastness properties, particularly or 2,3-dichloro-quinoxaline-6-sulphonyl radical and m is very good fastness to light. a number from to 2. In the following examples, which are given for the pur- Tetrazo components suitable for the production of polypose of illustrating the invention, the parts are parts by azo dyestuffs (Formula I, n=2) are, for example, l-ami- Weight, if not otherwise stated. no-4-(4' aminobenzoylamino)-benzene -2 sulphonic acid, N,N bis-(4 amino 3-sulphophenyl)-urea, N,N- EXAMPLE 1 bls ammo ',3I'SEIIPhOdIPhCDYIf4)urea 23.9 parts (0.1 mol) Z-amino-8-hydroxynaphthalene- (1 f [4 'b f 5-sulphonic acid (prepared according to the instructions Phomc ac1df4 Whlch may be Subsmuted the 10 of British patent specification No. 5148 [1894] are disbenzoyl radlcal q example by alkyl such as methyl solved neutral in 400 parts water and rendered acidic Examples of ammes of the formula RYNHZ are: to Congo with hydrochloric acid. The diazotisation mix- 1-amino-4-nitrobenzene-Z-sulphonic acid, ture, prepared in the usual manner from 21.8 parts (0.1 1amino-4-acylaminobenzene-Z-sulphonic acids, mol) 1-amino-4-nitrobenzene-2-sulphonic acid, is added h f 1 to this suspension at 0 C. and 140 parts by volume of a as or examp e sodium acetate solution are added dropwise in the 1-amino-4-acetylaminobenZene-2-sulphonic acid, course of 90 minutes. When the coupling is completed,

2-sulphonic acid, the product is salted out with sodium chloride and iso- 1-amino-4-(4'-nitrobenz0yl-amino)-benzene-2 lated.

sulphonic acid, 20 The resulting paste is dissolved neutral in 1000 parts 1-amino-4-(3'-nitrobenzoyl-amino)-benzene-2- water and mixed at 60 C. with a solution of 42 parts sulphonic acid, crystallised sodium sulphide in 100 parts water. When the 1-amino-4-(4'nitr0-3'-methylbenzoylamino)-benzene-2- reduction of the nitro group to the amino group is comsulphonic acid and l-amino-4-(4'-nitrobenzene pleted, the product is isolated acidic to Congo with sosulphonamido)-benzene-2-su1phonic a id, dium chloride and the paste freed from sulphur in the furthermore usual manner. Phosgene is then introduced at about C. into the solution of the aminoazo dyestuff, while the 4-amino-4'-(4"-nitrobenzoylarnino)-diphenyl-3- mixture is neutralised with a sodium carbonate solution,

sulphonic acid, until the formation of the urea of the formula lTlHz HzN N=NNHC O NH{N=N H aS 0H SOaH 80 11 HO- S3OH 4-amino-4'-(3"-nitrobenzoylamino)-dipheny1-3- sulphonic acid,

4-arnino-4-(3"-nitro-4"-methylbenzoylamino)- diphenyl-3-sulphonic acid,

is completed. The dyestuff is salted out, isolated and 40 dried. In the dried state, it is a dark powder which dissolves in water with a red-violet colour. The dyestuff 4 -4' 1 1 3- l i acid, dyes cotton in red-violet shades of very good fastness to 2-amino-6-nitro-naphthalene-4,8-disulphonic acid, g

4-amino-4'-nitrostilbene-2,2-disulphonic acid and If, instead of phosgene, terephthalic acid dichloride or 4-arnino-4'-acetylaminostilbene-2,2'-disulphonic acid. 5 fumaric acid dichloride is used as acylating agent, then dyestuffs are obtained which dye cotton in red-violet The new dyestuifs are valuable products which are very well suited for the dyeing and printing of hydroxyl groupand amido t i i fib materials, Further dyestufis of this type are set out in the followfor the dyeing of natural and regenerated cellulose, wool, f l The amino compound of the diaZO radical is silk, superpolyamide fibres and the like. The resulting E n In i116 first Column, the acylating agent in the shades.

dyeings, especially those on cellulose fibre materials, are ond column, and the colour shade in the third column.

Amino compound Acylating-agent Shade H NQ-NH-OOGNOZ Phosgene Purple.

soar: 7

Same as above 2,3-diehloroquinoxaline-ficarboxylie acid chloride Red-violet. Do Phenylisocyanate Purple. D0 P-ehlorophenylisocyante... Do.

Do m-Chlorophenyl isocyanate- Do. Do Furmarie acid dichloride Do H2NNHCOQ Phosgene Red-violet.

SOaH N02 CH3 H.N NH CO NO.

| SOaH HgNQ-NH-S 0 2( N O z 110. Red-violet.

Amino compound Acylating-agent Shade HQNQwIhOHQNHQ -..do Do.

A 01H H 038 mN- NH-C QQ-NO, Cyauurlc chloride Do.

(2:1) Same as Above Cyanuric chloride plus 3. N -methylaniline Do. Hz @-N QNO: Cyanuric chloride plus 2. p-sulphanilic acid plus 3. aniline Do. SOaH (1 1) V Same as above .l Cyanuric chloride plus 2. p-sulphanilic acid plus 3, N-methylaniline. Do.

. EXAMPLE 2 7 W and dried. In the dry state it is dark powder which dis- 31.9 parts (0.1 mol) 2amino-8-hydroxynaphthalene- 5,7-disulphonic acid' (prepared by sulphonating Z-amino- S-hydroxynaPhthalene-S- or -7-sulphonic acid in sulphuric acid 66 B. at 60 C.) are dissolved neutral in 350 parts 2 water, the solution is rendered acidic'with acetic acid,

combined with the diazotisation mixture of 0.1 mol 1-arnino-4-( l'-nitrobenzoylamino)-benzene 2 sulphonic acid at 0 C., 350 parts by volume of a 20% sodiumacetate solution are addeddropwise and 350parts by volume pyridineadded. When the coupling is completed, the dyestuif; is isolated acidicto Congo redissolved, if desired, in a soda-alkaline medium, and isolated.

The resulting paste is dissolved neutral in 1500 parts water and mixed at 55 to 60 C. with a solution of 36 parts crystallised sodium sulphide in 100 parts water.

When the reduction of the nitro group to the amino group is completed, the product is worked up'rin the usual man net and the aminoazo dyestul'f isolated. The dyestulf paste is dissolved in 2500 parts of warm water; phosgene is passed into the solution at 50 to 55 C., while neutralising with a sodium carbonate solution until the formation of the urea of the formula I SOaH 2 solves in water with a red-violet colour. The dyestuif dyescotton in red-violet fast shades.

If, instead of the above diazo component, the equivalent quantity of the aminodiphenyl compound of the 5 formula SOaH is used, then a disazo urea dyestutf is obtained which dissolves in water with a purple colour.

EXAMPLE 3 23.9 parts (0.1 mol) 2-amino-8-hydroxynaphthalene-5- sulphonic acid are dissolved neutral in 400 parts water, rendered acidic to Congo with a little hydrochloric-acid and mixed at 0 C. with a diazotisation mixture prepared from 0.1 mol acetylbenzidine monosulphonic acid of the formula SOaH SOaH Red-violet.

Purple.

EXAMPLE 4 A solution of 23.9 parts (0.1 mol) 2-amino-8-hydroxynaphthalene-S-sulphonic acid in 400 parts water is acidified with acetic acid (pH 4.5), combined at 5 to C. with the tetrazotisation mixture prepared in the usual manner from 0.05 mol 1-amino-4-(4'-aminobenzoylamino)- benzene-Z-sulphonic acid, and 500 parts by volume of a sodium acetate solution are added dropwise. When the coupling is completed, the product is salted out with sodium chloride and isolated. The dried dyestutf is a dark powder which dissolves in water with a red-violet colour;

Further dyestuffs which are produced by coupling with tetrazo components are set out in the following table:

We claim: v 1. An azo dyestuff of the formula:

| SOQH SOBH EXAMPLE 5 A soultion of 0.1 mol of the dyestuff of the formula i H0 38 O E S 0 3H (prepared by coupling, in an acetic acid medium, diazotised 1-a1nino-4-(4-nitrobenzoylamino) benzene 2-sulphonic acid with 2-amino-8-hydroxynaphthalene-S-sul1 Red-violet.

Purple.

Red (wool).

(1) nitro and (2) amino compounds of the formula:

wherein m is O or 1, and T is dichloropyrimidinyl, trichloropyrimidinyl Z-methylsulfonyl nicotinoyl, 2, 6-dichloroisonicotinoyl, 2,6-dimethylsulfonyl isonicotinoyl, 2,3 dichloroquinoxaline-6-canbonyl, 2,3-dichloroquinoXaline-6-sulfonyl, 2-p-sulfoanilino-4-anilino-1,3,5-triaiin-6 yl, or 2-p-sulfoanilino-4-N-methylanilino 133-;5-triazin-6-yl; and R when n is 2, is

. SO20 CH Q a 3,502,644 9 10 2. The dyestuif of claim 1 of the formula:

3. The dyestufi of claim 1 of the formula 1 References Cited UNITED STATES PATENTS 687,171 11/1901 Ulrich et a1. 260-175 1,173,077 2/1916 Ackermann 260175 1,901,515 3/1933 Hentrick et al. 260-199 2,053,817 9/1936 Felix et a1. 260199 XR 2,077,854 4/1937 Richard 260-199 3,002,964 10/1961 Keller et a1 260187 3,125,562 3/1964 Ammann et a1. 260-154 XR 3,211,554 10/1965 Dreyfus 260175 XR FLOYD D. HIGEL, Primary Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE Patent No.

Inventor(s) Horst Nickel, et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column Line 7 Table last formula (SEAL) Attcst:

Edward M. Fletcher, Ir. Attesting Officer L.

"2-sulphonic acid" should be deleted should read S'EP 291970 WHmIAM 2; 66m. JR. commissioner of Patents 

